EP0959058A1 - Hydrazinium nitroformate based high performance solid propellants - Google Patents

Hydrazinium nitroformate based high performance solid propellants Download PDF

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Publication number
EP0959058A1
EP0959058A1 EP98201696A EP98201696A EP0959058A1 EP 0959058 A1 EP0959058 A1 EP 0959058A1 EP 98201696 A EP98201696 A EP 98201696A EP 98201696 A EP98201696 A EP 98201696A EP 0959058 A1 EP0959058 A1 EP 0959058A1
Authority
EP
European Patent Office
Prior art keywords
hydrazinium nitroformate
propellant
hydroxyl terminated
propellant according
nitroformate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98201696A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jeroen Louwers
Petrus Johannes Maria Elands
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Original Assignee
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority to EP98201696A priority Critical patent/EP0959058A1/en
Priority to RU2000132232/02A priority patent/RU2220125C2/ru
Priority to EP99924052A priority patent/EP1086060B1/en
Priority to BR9910598-5A priority patent/BR9910598A/pt
Priority to CA002333211A priority patent/CA2333211C/en
Priority to US09/700,325 priority patent/US6916388B1/en
Priority to DE69921816T priority patent/DE69921816T2/de
Priority to IL13971699A priority patent/IL139716A/en
Priority to JP2000549560A priority patent/JP4057784B2/ja
Priority to AU40637/99A priority patent/AU759600B2/en
Priority to CNB998063878A priority patent/CN1329348C/zh
Priority to AT99924052T priority patent/ATE282016T1/de
Priority to PCT/NL1999/000307 priority patent/WO1999059940A1/en
Publication of EP0959058A1 publication Critical patent/EP0959058A1/en
Priority to ZA200006627A priority patent/ZA200006627B/en
Priority to NO20005824A priority patent/NO316834B1/no
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
    • C06B47/08—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant a component containing hydrazine or a hydrazine derivative
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • the present invention is directed to solid propellants for rocket motors, gas generators and comparable devices, based on a high energetic oxidizer, combined with a binder material.
  • Solid propellant combinations are prepared by blending solid oxidizers such as ammonium perchlorate or hydrazinium nitroformate with a liquid precursor for the matrix material. By curing of the binder a solid propellant is obtained, consisting of a polymer matrix and oxidiser in the form of solid inclusions.
  • solid oxidizers such as ammonium perchlorate or hydrazinium nitroformate
  • the present invention is based on the surprising discovery that it is possible to combine hydrazinium nitroformate with hydroxyl terminated unsaturated hydrocarbon compounds and accordingly the invention is directed to a solid propellant for rocket motors, comprising a cured composition of hydrazinium nitroformate and an unsatured hydroxyl terminated hydrocarbon compound.
  • a chemically stable solid propellant, with sufficient shelf life for practical use can be obtained, provided that hydrazinium nitroformate of high purity is used, which can, among others, be realized by improvements in the production process like the use of pure starting materials, containing substantially less impurities (e.g. chromium, iron, nickel, copper, and oxides of the metals, ammonia, aniline, solvent and the like).
  • impurities e.g. chromium, iron, nickel, copper, and oxides of the metals, ammonia, aniline, solvent and the like.
  • a further improvement in the stability of the solid propellant can be obtained by using hydrazinium nitroformate which contains substantially no hydrazine or nitroform in unreacted form.
  • This can for example be obtained by changes in the production process, as discussed in WO-A 9410104 and a strict control of the addition rate of hydrazine and nitroform during the production of hydrazinium nitroformate, resulting in a purity of the recrystallised hydrazinium nitroformate between 98.8 and 100.3, based on H 3 O + and a pH-value of a 10 wt.% aqueous solution of hydrazinium nitroformate of at least 4.
  • the water content of the different propellant ingredients influences the stability and accordingly a water content of less than 0.01 wt.% in the binder is preferred.
  • stabilisers may be added to further improve the shelf-life.
  • the solid propellant combinations according to the invention have various advantages. They possess an increased performance, expressed as an increased specific impulse for rocket applications and as an increased ramjet specific impulse for gasgenerator applications.
  • ⁇ is the weight mixture ratio of air and gas generator propellant
  • I sp is the specific impulse with ambient air as one of the propellant ingredients
  • U 0 is the velocity of the incoming air.
  • the material is chlorine free, which is an advantage from both corrosion and environmental considerations.
  • a solid propellant can comprise 80 to 90 wt.% of hydrazinium nitroformate, in combination with 10 to 20 wt.% of binder (hydroxyl terminated unsaturated hydrocarbon and other standard binder components, such as curatives, plasticisers, crosslinking agents, chain extenders and anti-oxidants).
  • binder hydroxyl terminated unsaturated hydrocarbon and other standard binder components, such as curatives, plasticisers, crosslinking agents, chain extenders and anti-oxidants.
  • a fuel additive such as aluminium
  • 10 to 20% of the hydrazinium nitroformate in the above composition can be replaced by the additive.
  • a gas generator propellant for ramjets or ducted rockets the following combinations are preferred. 20 to 50 wt.% of hydrazinium nitroformate, combined with 50 to 80 wt.% of hydroxyl terminated unsatured hydrocarbon.
  • an amount of fuel additive for increased performance such as Al, B, C and B 4 C, whereby this fuel additive may be present in 10 to 70 wt.%, in combination with 10 to 70 wt.% of the hydrocarbon, keeping the amount of hydrazinium nitroformate identical.
  • the solid propellant is prepared from a cured composition of hydrazinium nitroformate and a hydroxyl terminated unsatured hydrocarbon.
  • the hydrazinium nitroformate preferably has the composition described above, whereby the amount of impurities is kept at a minimum.
  • the binder or polymeric matrix material is prepared from a hydroxyl terminated unsaturated hydrocarbon.
  • this hydrocarbon preferably has a low molecular weight, making it castable, even when containing substantial amounts of solids.
  • a suitable molecular weight for the hydrocarbon ranges from 2000 to 3500 g/mol.
  • Suitable polyisocyanates are isophorone-di-isocyanate, Desmodur N-100, MDI, TDI, and other polyisocyanates known for use in solid propellant formulations, as well as combinations thereof.
  • the amounts thereof are preferably selected in dependence of the structural requirements so that the ratio of hydroxyl groups in the hydrocarbon and the isocyanates is between 0.7 and 1.2.
  • Curing conditions are selected such that an optimal product is obtained by modifying temperature, curing time, catalyst type and catalyst content. Examples of suitable conditions are curing times between 3 and 14 days, temperatures between 30 and 70°C and use of small amounts of cure catalysts, such as DBTD ( ⁇ 0.05 wt.%)
  • Example 1 HNF/HTPB as a high performance propellant composition.
  • HNF/HTPB as a high performance fuel for a ducted rocket gas generator for ramjet applications.
  • Table 2 the ramjet specific impulses of a 30% and a 40% solids HNF/HTPB are listed in comparison to 40% solids AP/HTPB fuel and a GAP fuel. The latter two represent typical state-of-the-art fuels for ducted rocket gas generator propellants.
  • ducted rockets fuel rich reaction products of a propellant are injected into a combustion chamber where it reacts with oxygen from the incoming air.
  • HNF/HTPB compositions possess higher ramjet specific impulses compared to other compositions which are momentary under consideration for ramjet fuel applications.
  • HNF/HTPB has the additional advantages that it has a low signature (HCl free exhaust), potentially a high pressure exponent, n, increasing the gas generator throtteability and possibly lower oxidator loadings compared to AP-based gas generators, resulting in overall performance gains.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Medicinal Preparation (AREA)
EP98201696A 1998-05-20 1998-05-20 Hydrazinium nitroformate based high performance solid propellants Withdrawn EP0959058A1 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
EP98201696A EP0959058A1 (en) 1998-05-20 1998-05-20 Hydrazinium nitroformate based high performance solid propellants
IL13971699A IL139716A (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
JP2000549560A JP4057784B2 (ja) 1998-05-20 1999-05-19 ヒドラジニウムニトロホルメートを主成分とする高性能固体推進剤
BR9910598-5A BR9910598A (pt) 1998-05-20 1999-05-19 Prolente sólido para motores de foguete, geradores de gás e dispositivos comparáveis, e, uso de uma composição curada de nitroformamiato de hidrazìnio e um composto hidrocarboneto insaturado terminado em hidroxila
CA002333211A CA2333211C (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
US09/700,325 US6916388B1 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
DE69921816T DE69921816T2 (de) 1998-05-20 1999-05-19 Hochleistungsfesttreibstoff auf basis von hydrazin-nitroform
RU2000132232/02A RU2220125C2 (ru) 1998-05-20 1999-05-19 Твердое ракетное топливо высокой эффективности на основе нитроформата гидразина
EP99924052A EP1086060B1 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
AU40637/99A AU759600B2 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
CNB998063878A CN1329348C (zh) 1998-05-20 1999-05-19 基于硝基甲酸的高性能固体推进剂
AT99924052T ATE282016T1 (de) 1998-05-20 1999-05-19 Hochleistungsfesttreibstoff auf basis von hydrazin-nitroform
PCT/NL1999/000307 WO1999059940A1 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants
ZA200006627A ZA200006627B (en) 1998-05-20 2000-11-15 Hydrazinium nitroformate based high performance solid propellants.
NO20005824A NO316834B1 (no) 1998-05-20 2000-11-17 Hydraziniumnitroformatbasert drivmiddel med hoy ytelse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP98201696A EP0959058A1 (en) 1998-05-20 1998-05-20 Hydrazinium nitroformate based high performance solid propellants

Publications (1)

Publication Number Publication Date
EP0959058A1 true EP0959058A1 (en) 1999-11-24

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP98201696A Withdrawn EP0959058A1 (en) 1998-05-20 1998-05-20 Hydrazinium nitroformate based high performance solid propellants
EP99924052A Expired - Lifetime EP1086060B1 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP99924052A Expired - Lifetime EP1086060B1 (en) 1998-05-20 1999-05-19 Hydrazinium nitroformate based high performance solid propellants

Country Status (14)

Country Link
US (1) US6916388B1 (ja)
EP (2) EP0959058A1 (ja)
JP (1) JP4057784B2 (ja)
CN (1) CN1329348C (ja)
AT (1) ATE282016T1 (ja)
AU (1) AU759600B2 (ja)
BR (1) BR9910598A (ja)
CA (1) CA2333211C (ja)
DE (1) DE69921816T2 (ja)
IL (1) IL139716A (ja)
NO (1) NO316834B1 (ja)
RU (1) RU2220125C2 (ja)
WO (1) WO1999059940A1 (ja)
ZA (1) ZA200006627B (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6454886B1 (en) 1999-11-23 2002-09-24 Technanogy, Llc Composition and method for preparing oxidizer matrix containing dispersed metal particles
US6503350B2 (en) 1999-11-23 2003-01-07 Technanogy, Llc Variable burn-rate propellant
CN101338236B (zh) * 2008-08-12 2012-02-22 浙江大学 一种含聚二茂铁基化合物燃速促进剂的推进剂及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2511370C2 (ru) * 2012-07-04 2014-04-10 Николай Евгеньевич Староверов Ракетное топливо или взрывчатое вещество и способ его приготовления (варианты)
RU2552745C1 (ru) * 2013-11-19 2015-06-10 Николай Евгеньвич Староверов Взрывчатое вещество (варианты)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658608A (en) * 1970-09-23 1972-04-25 Nasa Hydrazinium nitroformate propellant stabilized with nitroguanidine
US3708359A (en) * 1970-09-23 1973-01-02 Nasa Hydrazinium nitroformate propellant with saturated polymeric hydrocarbon binder
EP0194180A1 (fr) * 1985-02-27 1986-09-10 Societe Nationale Des Poudres Et Explosifs Procédé de fabrication sans solvants de produits pyrotechniques composites à liant thermodurcissable
EP0350135A2 (en) * 1988-07-08 1990-01-10 European Space Agency High-performance propellant combinations for a rocket engine
GB2228731A (en) * 1979-08-14 1990-09-05 Poudres & Explosifs Ste Nale Autopyrolysable propellant composition
WO1994010104A1 (en) * 1992-11-03 1994-05-11 Aerospace Propulsion Products B.V. Method of preparing hydrazine nitroform
US5320692A (en) * 1981-11-25 1994-06-14 The United States Of America As Represented By The Secretary Of The Navy Solid fuel ramjet composition

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US3837940A (en) * 1963-02-28 1974-09-24 Exxon Research Engineering Co Ignitor containing polymeric nf{11 -adducts
JPS5663898A (en) * 1979-10-24 1981-05-30 Nissan Motor Polyene type composite propellant caking agent
US4658578A (en) * 1984-01-10 1987-04-21 Morton Thiokol Inc. Igniting rocket propellants under vacuum conditions
JP3360177B2 (ja) * 1991-07-04 2002-12-24 アジャンス スパシアル エウロペンヌ 特にロケット等の輸送手段の推進のための推進薬及びその製造方法
US5472532A (en) * 1993-06-14 1995-12-05 Thiokol Corporation Ambient temperature mix, cast, and cure composite propellant formulations
WO2001029111A1 (en) * 1999-10-19 2001-04-26 Alliant Techsystems Inc. Polymerization of poly(glycidyl nitrate) from high purity glycidyl nitrate synthesized from glycerol

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US3658608A (en) * 1970-09-23 1972-04-25 Nasa Hydrazinium nitroformate propellant stabilized with nitroguanidine
US3708359A (en) * 1970-09-23 1973-01-02 Nasa Hydrazinium nitroformate propellant with saturated polymeric hydrocarbon binder
GB2228731A (en) * 1979-08-14 1990-09-05 Poudres & Explosifs Ste Nale Autopyrolysable propellant composition
US5320692A (en) * 1981-11-25 1994-06-14 The United States Of America As Represented By The Secretary Of The Navy Solid fuel ramjet composition
EP0194180A1 (fr) * 1985-02-27 1986-09-10 Societe Nationale Des Poudres Et Explosifs Procédé de fabrication sans solvants de produits pyrotechniques composites à liant thermodurcissable
EP0350135A2 (en) * 1988-07-08 1990-01-10 European Space Agency High-performance propellant combinations for a rocket engine
WO1994010104A1 (en) * 1992-11-03 1994-05-11 Aerospace Propulsion Products B.V. Method of preparing hydrazine nitroform

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Title
CHEMICAL ABSTRACTS, vol. 122, no. 2, 9 January 1995, Columbus, Ohio, US; abstract no. 13156t, A.C. HORDIJK ET AL.: "Properties of hydrazine nitroformate; a "new" oxidizer for high performance solid propellants." page 187; XP000660506 *
CHEMICAL ABSTRACTS, vol. 123, no. 14, 2 October 1995, Columbus, Ohio, US; abstract no. 174351p, ANAN TOSHIYUKI ET AL.: "Physical and chemical properties of HNF" page 281; XP000663569 *
CHEMICAL ABSTRACTS, vol. 123, no. 22, 27 November 1995, Columbus, Ohio, US; abstract no. 291160m, H.F.R. SCHOYER ET AL.: "High-performance propellants based on hydrazinium nitroformate" page 324; XP000663426 *
Int. Annu. Conf. ICT 1994, 25TH(energetic materials-analysis, characterization and test techniques), 69/1-69/11 *
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KAYAKU GAKKAISHI, vol. 56, no. 3, 1995, pages 99 - 104 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6454886B1 (en) 1999-11-23 2002-09-24 Technanogy, Llc Composition and method for preparing oxidizer matrix containing dispersed metal particles
US6503350B2 (en) 1999-11-23 2003-01-07 Technanogy, Llc Variable burn-rate propellant
CN101338236B (zh) * 2008-08-12 2012-02-22 浙江大学 一种含聚二茂铁基化合物燃速促进剂的推进剂及其制备方法

Also Published As

Publication number Publication date
JP4057784B2 (ja) 2008-03-05
RU2220125C2 (ru) 2003-12-27
CA2333211A1 (en) 1999-11-25
NO316834B1 (no) 2004-05-24
ZA200006627B (en) 2001-10-31
EP1086060A1 (en) 2001-03-28
IL139716A (en) 2004-07-25
WO1999059940A1 (en) 1999-11-25
AU759600B2 (en) 2003-04-17
ATE282016T1 (de) 2004-11-15
AU4063799A (en) 1999-12-06
EP1086060B1 (en) 2004-11-10
DE69921816D1 (de) 2004-12-16
CN1329348C (zh) 2007-08-01
NO20005824D0 (no) 2000-11-17
US6916388B1 (en) 2005-07-12
JP2002515399A (ja) 2002-05-28
DE69921816T2 (de) 2005-12-01
BR9910598A (pt) 2001-01-16
IL139716A0 (en) 2002-02-10
CA2333211C (en) 2008-07-22
NO20005824L (no) 2000-11-27
CN1301243A (zh) 2001-06-27

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